Polymer containing a succinimide ring substituted on the nitrogen atom by a reactive group

ABSTRACT

A polymer contains a succinimide ring substituted on the nitrogen atom by a reactive group, where the ring is supported either by the main chain or by a side chain, the polymer resulting from reacting at least one polyolefin with at least one compound containing a maleimide ring substituted on the nitrogen atom by a reactive group with formula —R—(X) n  where X is a reactive group, n is a whole positive number equal to 1 or more and R is a residue containing at least one carbon atom. These polymers can be used for the production of co-extruded products, multi-layered materials, surface coatings and polymer alloys.

This is a continuation, of application Ser. No. 08/988,988 filed Dec.11, 1997, now U.S. Pat. No. 6,184,303.

The present invention concerns polymers containing at least onesuccinimide ring substituted on the nitrogen atom by a reactive group,where the ring is supported either by the main chain or by a side chain.

The properties of the polymers of the present invention are improvedcompared with polymers which do not contain a succinimide ringsubstituted on the nitrogen atom by a reactive group. In particular,they have improved adhesive properties and can thus be used as surfacecoatings. They are also more heat resistant than the polymers from whichthey are derived.

The polymers of the present invention have reactive groups which allowthem to be used in the production of polymer alloys.

The polymers of the present invention can be defined as polymerscontaining at least one succinimide ring substituted on the nitrogenatom by a reactive group, the ring being supported either by the mainchain or by a side chain, the polymers resulting from reacting at leastone polyolefin obtained from at least one unsaturated monomer selectedfrom ethylene, butenes and norbornenes, with at least one compoundcontaining a maleimide ring substituted on the nitrogen atom by areactive group with formula —R—(X)_(n) where X is a reactive group, n isa number equal to 1 or more and R is a residue containing at least onecarbon atom. Usually, n equals 1 and in this case the compoundcontaining a maleimide ring used in the present invention is representedby formula 1 below:

The reactive group —X is generally selected from a hydroxyl group, acarboxylic group, a carboxamide group, a carboxylic acid halide group, athiol group, a thiocarboxylic group, an amino group, a halogen, an epoxygroup, and an esterified carboxylic group in which the ester portioncontains a reactive group. When a plurality of —X groups are present,they can be identical or different.

Very often, the reactive group is selected from groups which can reactwith epoxy functions by opening the oxirane ring. Usually, compoundscontaining a reactive group are used which are selected from acarboxylic group, a carboxamide group and an acid halide group, forexample a carboxylic acid chloride group. The preferred group is thecarboxylic group.

The group —R— is normally selected from the group formed by saturated orunsaturated, substituted or unsubstituted aliphatic hydrocarbons, andsubstituted or unsubstituted aromatic groups. In general, unsubstitutedgroups are preferred, normally groups containing at least one aromaticnucleus. Examples of groups which are frequently used are benzenicgroups which are bonded in the ortho, meta or para position to thenitrogen atom and to the reactive group —X. Normally, the para or metaform is used.

The polyolefins used to produce the polymers of the present inventioncan be formed by homopolymerisation or copolymerisation of at least twomonomers.

In one particularly preferred form, the polyolefin is selected from thegroup formed by high density polyethylenes and ethylene copolymers whichare preferably constituted by at least 90% of ethylene moieties and atmost 10% of a C₃ to C₈ olefin. More particularly, high densitypolyolefins are used which preferably have a density of about 0.9 toabout 0.97 and a fusion index measured in accordance with standard ASTMD-1238 of about 0.2 to about 100 (measurements carried out under a 19.6kg load at 190° C.).

The polymers of the present invention are prepared bringing a moltenpolyolefin into contact with at least one compound containing amaleimide ring substituted on the nitrogen atom by a reactive group in amixer or extruder. This preparation can be carried out with or without aradical initiator. Examples of radical initiators are peroxides.Preferably, a radical initiator is not used in the present invention.This possibility of forming, without a radical initiator, polymerscontaining a succinimide ring substituted on the nitrogen atom by areactive group, the ring being supported either by the principal chainor by a side chain, constitutes a distinct advantage of the presentinvention which avoids the risk of cleavage and cross-linking of thepolymer. The reaction temperature is normally in the range from aboutthe fusion temperature of the polyolefin to about 300° C. Thistemperature is usually about 200° C. to about 260° C. The reaction timeis relatively short and normally does not exceed 10 minutes. Anextrusion-reaction system is normally preferable as it produces verygood results.

The present invention also concerns the use of the polymers describedabove for the production of surface coatings. These polymers, with goodadhesive properties, are more suitable than the starting polyolefins forthis application. These polymers can also be used to produce alloys ofpolymers, in which the reactive function improves formation of thealloys. They can also be used for the production of co-extrudedproducts. They can also be used for the production of multi-layeredmaterials.

The following examples illustrate the invention without limiting itsscope.

EXAMPLE 1

This example describes the preparation of a grafted polymer in a mixer.

42.5 grams (g) of medium density polyethylene (d=0.954) sold by FINAunder the trade name Finathene 3802® and 0.42 g of 4-maleimidobenzoicacid (AMB) were introduced into a Haake Rheocord® kneader. The workingtemperature was 240° C., the blade rotation rate was 64 revolutions perminute (rpm). After 5 minutes of mixing at 240° C., the reaction productwas cooled in water and dried at 60° C. under 1 millimeter (mm) ofmercury for 8 hours. The product obtained was used for adhesion tests,the results of which are shown in Table 1 below.

EXAMPLE 2

The procedure described in Example 1 was repeated, using 1.7 g of AMB,i.e., 2.5% by weight. The product obtained was used in adhesion tests,the results of which are shown in Table 1 below.

EXAMPLE 3

This example describes the preparation of a grafted polymer using aCLEXTRAL co-rotating twin screw extruder sold under the trade name BC21,with a length/diameter ratio of 28, a screw diameter of 25 mm and,provided with a 4 mm diameter die.

Granules of Finathene 3802® polyethylene and a quantity corresponding to1% by weight of AMB with respect to the polyethylene were simultaneouslyintroduced into the supply hopper of the extruder.

The total rate at which the products were introduced into the extruderwas 5 kilograms per hour and the reaction temperature in the extruderwas held at 240° C. The screw rotation speed was 100 rpm, the residencetime was 1 minute. The rod leaving the die was cooled in water at 25°C., granulated and dried for the adhesion tests.

EXAMPLE 4

The procedure described in Example 3 was repeated, using 2% by weight ofAMB. The product obtained was used in adhesion tests, the results ofwhich are shown in Table 1 below.

EXAMPLE 5

Adhesion tests were carried out on the various products using metallicaluminium specimens.

The adhesive properties of the compositions were determined using theASTM D 1002 method.

The test procedure comprised preparing metallic specimens. 600 cm³ ofchromic-sulphuric acid mixture was prepared and a series of specimenswas placed on a support then immersed in a receptacle containing thechromic-sulphuric acid mixture which was held at a temperature of 60° C.After 15 minutes, the samples were withdrawn. They were rinsed withplenty of water and oven dried for 2 hours at 80° C.

An adhesive bonding surface 25.4 mm×12.7 mm was delimited on a specimenand a maximum adhesive joint thickness of 125×10⁻⁶ m was delimited usingshims. Two specimens were adhesively bonded using a DARRAGON table presspreheated to 200° C., applying a pressure of 0.5 MPa for 5 minutes.

A traction test was then carried out with an INSTRON type machineprovided with a measuring head of 10⁵ Newton. The rate of displacementof the beam was 1 mm/min.

The results of the adhesion tests are given in Table 1 below. The valuesgiven correspond to an average value obtained over 10 successive tests.By way of comparison, tests were carried out on medium densitypolyethylene HDPE Finathene 3802® and with a terpolymer sold by ORKEMwith reference Lotader 3210® with a number average molecular mass of15050 and a polydispersity index of 5.3.

TABLE 1 Breaking load in Nature of tested polymer kiloNewton (kN) Natureof break HDPE 2.1 adhesive Lotader 3210 ® 2.7 adhesive Product fromexample 1 4.2 cohesive Product from example 2 3.9 cohesive Product fromexample 3 4.3 cohesive Product from example 4 4.0 cohesive

The large increase in the maximum load necessary to cause breaking whenusing the products of the present invention can be seen, also thedifference in the nature of the break which occurs in the mass and whichdemonstrates the large improvement in adhesion obtained with theproducts of the invention.

What is claimed is:
 1. A polymer containing at least one succinimidering substituted on the nitrogen atom by a reactive group, said ringbeing supported either by the main chain or by a side chain, saidpolymer being a reaction product resulting from reacting a polyolefinbeing a high density polyethylene selected from the group consisting ofa homopolymer of ethylene, a copolymer of ethylene constituted by atleast 90% by weight of ethylene moieties and at most 10% by weight of aC₃ to C₈ olefin, and a polymer of a norbornene, with at least onecompound containing a maleimide ring substituted on the nitrogen atom bya reactive group with formula —R—(X)_(n) where X is a carboxylic group,n is a number equal to 1 or more and R is a residue containing at leastone carbon atom.
 2. A polymer consisting essentially of at least onesuccinimide ring substituted on the nitrogen atom by a reactive group,said ring being supported either by the main chain or by a side chain,said polymer being a reaction product resulting from reacting apolyolefin being a high density polyethylene selected from the groupconsisting of a homopolymer of ethylene, a copolymer of ethyleneconstituted by at least 90% by weight of ethylene moieties and at most10% by weight of a C₃ to C₈ olefin, and a polymer of a norbornene, withat least one compound containing a maleimide ring substituted on thenitrogen atom by a reactive group with formula —R—(X)_(n) where X is areactive group selected from a carboxylic group, n is a number equal to1 or more and R is a residue containing at least one carbon atom.
 3. Apolymer consisting of at least one succinimide ring substituted on thenitrogen atom by a reactive group, said ring being supported either bythe main chain or by a side chain, said polymer being a reaction productresulting from reacting a polyolefin being a high density polyethyleneselected from the group consisting of a homopolymer of ethylene, acopolymer of ethylene constituted by at least 90% by weight of ethylenemoieties and at most 10% by weight of a C₃ to C₈ olefin, and a polymerof a norbornene, with at least one compound containing a maleimide ringsubstituted on the nitrogen atom by a reactive group with formula—R—(X)_(n) where X is a reactive group selected from a carboxylic group,n is a number equal to 1 or more and R is a residue containing at leastone carbon atom.
 4. A polymer according to claim 1, in which group —R—is selected from a saturated or an unsaturated, a substituted or anunsubstituted aliphatic hydrocarbon, or a substituted or anunsubstituted aromatic group.
 5. A polymer according to claim 1, inwhich the polyolefin is a copolymer of ethylene constituted by at least90% by weight of ethylene moieties and at most 10% of a C₃ to C₈ olefin.6. A polymer according to claim 1 in which the group —R— is a benezeneresidue and the group —X is in the position para to the nitrogen atom.7. A process for the preparation of a polymer according to claim 1comprising contacting a molten polyolefin in a mixer or extruder with atleast one compound containing a maleimide ring substituted on a nitrogenatom by a reactive group.
 8. A surface coating comprising a polymeraccording to claim
 1. 9. A polymer alloy comprising a polymer accordingto claim
 1. 10. A co-extruded product comprising a polymer according toclaim
 1. 11. A multi-layered product comprising a polymer according toclaim
 1. 12. A polymer prepared in accordance with the process of claim1.